EP1359184B1 - Feuille en polyester thermorétractable - Google Patents

Feuille en polyester thermorétractable Download PDF

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Publication number
EP1359184B1
EP1359184B1 EP03015681A EP03015681A EP1359184B1 EP 1359184 B1 EP1359184 B1 EP 1359184B1 EP 03015681 A EP03015681 A EP 03015681A EP 03015681 A EP03015681 A EP 03015681A EP 1359184 B1 EP1359184 B1 EP 1359184B1
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EP
European Patent Office
Prior art keywords
film
shrinkage
heat shrinkable
packs
shrinkable polyester
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP03015681A
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German (de)
English (en)
Other versions
EP1359184A1 (fr
Inventor
Hideki Ito
Masatosi Hashimoto
Yukinobu Mukouyama
Norimi Tabota
Tsutomu Oko
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Toyobo Co Ltd
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Toyobo Co Ltd
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Filing date
Publication date
Priority claimed from JP2083699A external-priority patent/JP3278058B2/ja
Priority claimed from JP6089899A external-priority patent/JP2000254968A/ja
Priority claimed from JP11733999A external-priority patent/JP2000309647A/ja
Priority claimed from JP11734099A external-priority patent/JP2000301609A/ja
Priority claimed from JP11733899A external-priority patent/JP2000309646A/ja
Application filed by Toyobo Co Ltd filed Critical Toyobo Co Ltd
Publication of EP1359184A1 publication Critical patent/EP1359184A1/fr
Application granted granted Critical
Publication of EP1359184B1 publication Critical patent/EP1359184B1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]

Definitions

  • the present invention relates to a heat shrinkable polyester film, and particularly to a heat shrinkable polyester film suitable for use in a label. More particularly, the present invention relates to a heat shrinkable polyester film for use in a multi-packaging label for packaging, inter alia, a stack of cans, which has a good shock resistance during shipping, especially under low temperatures, with a good finish after shrinkage and a sufficient solvent adhesiveness (i.e. , an adhesive property of the film provided by application of a solvent thereon).
  • Heat shrinkable films made of polyvinyl chloride, polystyrene, or the like have been widely used in the field of multi-packaging films for use in packaging a stack of cans.
  • heat shrinkable polyester films have been attracting public attention as more problems have been found to exist with the former materials. That is, polyvinyl chloride products generate a chlorine gas when incinerated, and it is difficult to print on polystyrene products.
  • One possible way to prevent such tearing along a particular direction is to orient a film along a direction perpendicular to its main shrinkage direction as well as the main shrinkage direction.
  • the film may be shrunk with a poor balance between the directions, thereby resulting in a poor finish after shrinkage.
  • a tube is produced from the film by using an environmentally preferred chlorine-free solvent, a sufficient solvent adhesiveness cannot be obtained.
  • a container e.g., a bottle
  • a so-called “cap seal” wrapped around the cap or lid of the container is provided not only for decorative purposes but also for purposes of preventing someone from mixing poison into the contained product.
  • a heat shrinkable film of polyvinyl chloride, polystyrene, or the like has been widely used in a cap sealing label, as in a general purpose label.
  • polyvinyl chloride products generate a chlorine gas when incinerated, and it is difficult to print on polystyrene products).
  • a cap seal may be produced as follows. First, a sheet of heat shrinkable film having a predetermined size is rolled into a tubular shape with two of its opposite edges bonded together. Then, the tubular film is cut into smaller tubular label pieces.
  • One way is to directly place a label produced as described above around the container and shrink the label onto the container.
  • the other way is to first shrink the label onto a metal mold to provide a "preform" product, and then further shrink the label onto the container.
  • the label when the label is heat-shrunk; the bonded portion (backlining portion) of the label desirably stays bonded together. If the bonded portion falls apart, the productivity decreases substantially.
  • the shape characteristics of the label after it is heat-shrunk are also important. It is undesirable that the label does not shrink enough, or the shrunk label has creasage, shrinkage non-uniformity, distortion, or jumping. Particularly when the label is used for a food container, it is in many cases undesirable for the label to get moist. Therefore, in such a case, the heat shrinkage process is typically done using hot air instead of steam. When using hot air, however, the heat efficiency is lower than that when using steam, whereby it is likely that the film does not shrink enough, or the shrunk label has creasage, shrinkage non-uniformity, distortion.
  • EP 0 267 799 A2 describes a shrinkable polyester film for applying to bottles and other articles comprising not less than 50 mol% of ethylene terephthalate units and having a birefringence of from 0.040 to 0.150, a shrinkage of not less than 40% in one of the machine direction and the transverse direction and a shrinkage of not more than 20% in the other of said directions after 5 min treatment in an oven at 100°C, and a heat of fusion of not less than 8.37 kJ/kg (2 cal/g).
  • the film is also required to have transparency.
  • a heat shrinkable polyester film has a transverse tear defect percentage of 20% or less as determined in the following vibration test: the film is rolled into a tubular shape, two of its opposite edges bonded together, and then the tubular film is placed around a vertical stack (total weight: 660 g) of three food container cans each having a diameter of 72 mm and a height of 55 mm; the can stack with the tubular film placed therearound is passed through a shrink tunnel to shrink the tubular film onto the can stack; a total of 18 packs of such can stacks are placed into a cardboard box having a length of 455 mm, a width of 230 mm and a height of 165 mm (6 packs in the length direction by 3 packs in the width direction), and the cardboard box is sealed; the cardboard box is vibrated along the width direction for 30 min by a stroke of 50 mm and at a vibration rate of 180 reciprocations/min, after which the transverse tearage of the tubular film is visually observed; and the transverse tear defect percentage (%) is
  • the film has a longitudinal refractive index Nx and a transverse refractive index Ny which satisfy the following expressions (1) and (2): 1.561 ⁇ Nx ⁇ 1.566 and 0.040 ⁇ Ny - Nx ⁇ 0.070 the film has a shrinkage of 50% or more along its main shrinkage direction when the film is put in hot water of 95° C for 10 sec, and the film has a shrinkage of 10% to 25% along a direction perpendicular to its main shrinkage direction when the film is put in hot water of 95° C for 10 sec.
  • the film has a solvent adhesiveness with 1,3-dioxolane.
  • the film can be used as a multi-packaging film.
  • the invention described herein makes possible the advantages of: (1) providing a heat shrinkable polyester film which has a good shock resistance during shipping especially under low temperatures, with a good finish after shrinkage and a sufficient solvent adhesiveness; and (2) providing a heat shrinkable polyester film having such properties for use in a multi-packaging label for packaging, inter alia, a stack of cans.
  • a heat shrinkable polyester film according to an embodiment of the present invention will now be described.
  • Preferred polyesters for use in a heat shrinkable polyester film of the present invention suitable for use as a multi-packaging film typically include polyethylene terephthalate, polyethylene naphthalate, and other polyesters obtained by copolymerizing such polyesters with an acid component or a long-chain glycol component of an aliphatic compound.
  • the polyester comprising terephthalic acid or naphthalenedicarboxylic acid
  • dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, isophthalic acid, decanedicarboxylic acids, and dimer acid.
  • diol component comprising butanediol
  • diol component comprising butanediol
  • diols such as ethylene glycol, neopentyl glycol, hexamethylene glycol, 1,4-cyclohexane dimethanol, dimer acid diol, and ethylene-oxide-added tetramethylene glycol.
  • neopentyl glycol as one of the diol components.
  • the film preferably contain an inorganic lubricant and/or an organic lubricant.
  • the film may contain further additives such as a stabilizer, a coloring agent, an antioxidant, a defoamer, and an antistatic agent.
  • the heat shrinkable polyester film of the present invention is required to have a transverse tear defect percentage of 20% or less, and preferably about 10% or less, as determined in a vibration test. When the transverse tear defect percentage exceeds 20%, the film is likely to have many tears during actual shipping.
  • the refractive indices Nx, Ny of the film satisfies the following expressions (1) and (2): 1.561 ⁇ Nx ⁇ 1.566 and 0.040 ⁇ Ny - Nx ⁇ 0.070
  • the more preferred range of the refractive index Nx is 1.562 to 1.565.
  • the more preferred range of the value (Ny-Nx) is 0.050 to 0.060.
  • the refractive index Nx is less than 1.561, the strength of the film against transverse tears may be insufficient.
  • the refractive index Nx exceeds 1.566, the shrinkage of the film along a direction perpendicular to the main shrinkage direction increases, thereby decreasing the shrunk finish property.
  • the film of the present invention has a shrinkage of 50% or more, and more preferably about 55% or more, along its main shrinkage direction when the film is put in hot water of 95° C for 10 sec.
  • a shrinkage 50% or more, and more preferably about 55% or more, along its main shrinkage direction when the film is put in hot water of 95° C for 10 sec.
  • the film of the present invention has a shrinkage of 10% to 25%, and more preferably about 10 % to about 20 % , along a direction perpendicular to its main shrinkage direction when the film is put in hot water of 95° C for 10 sec.
  • the hot water shrinkage along this direction is less than 10%, the strength of the film against transverse tears may be insufficient.
  • hot water shrinkage along this direction exceeds 25%, the shrunk film may have shrinkage non-uniformity or jumping, thereby resulting in a poor finish.
  • the film of the present invention has a solvent adhesiveness with 1,3-dioxolane.
  • a polyester film having its main shrinkage direction along the transverse (or width) direction is more practical. Therefore, an exemplary film production method where the film has its main shrinkage direction along the transverse direction will be described below. However, it is understood that the present invention is also applicable to a case where the film has its main shrinkage direction along the longitudinal direction.
  • a polyester material is first dried by using a dryer or vacuum dryer such as a hopper dryer or a paddle dryer. Then, the polyester material is extruded at a temperature of 200°C to 300°C, and rapidly cooled to obtain an undrawn film.
  • the obtained undrawn film is typically drawn longitudinally by a drawing factor of 1.1 to 1.3 at 80°C to 95°C, and then drawn laterally by a drawing factor of 3 to 5 at 70°C to 85°C. It is understood that any other drawing condition may alternatively be set for this process.
  • the dicarboxylic acid component of the polyester may include aromatic dicarboxylic acids (e:g., terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and orthphthalic acid), aliphatic dicarboxylic acids (e.g., adipic acid, azelaic acid, sebacic acid, and decanedicarboxylic acids), alicyclic dicarboxylic acids, or the like.
  • aromatic dicarboxylic acids e:g., terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and orthphthalic acid
  • aliphatic dicarboxylic acids e.g., adipic acid, azelaic acid, sebacic acid, and decanedicarboxylic acids
  • alicyclic dicarboxylic acids e.g., adipic acid, azelaic acid, sebacic acid, and decanedicarboxy
  • the polyester contains an aliphatic dicarboxylic acid(s) (e.g., adipic acid, sebacic acid, decanedicarboxylic acid, or the like)
  • the content of the aliphatic dicarboxylic acid is preferably less than 3 mol% (this applies to all the dicarboxylic acid components used).
  • a heat shrinkable polyester film obtained by using a polyester which contains 3 mol% or more of such an aliphatic dicarboxylic acid (s) may not have a sufficient rigidity in high-speed processes.
  • the polyester preferably does not contain a polyvalent carboxylic acid whose valence is 3 or more (e. g. , a trimellitic acid, a pyromellitic acid, or anhydride thereof). If the polyester contains such a polyvalent carboxylic acid, the content thereof is preferably 3 mol% or less. With a heat shrinkable polyester film obtained by using a polyester containing such a polyvalent carboxylic acid, a sufficient shrinkage may not be achieved.
  • a diol component of the polyester to be used in the present invention may include aliphatic diols (e.g., ethylene glycol, propane diol, butane diol, neopentyl glycol, hexane diol, or the like), alicyclic diols (e.g., 1,4-cyclohexane dimethanol), aromatic diols, or the like.
  • aliphatic diols e.g., ethylene glycol, propane diol, butane diol, neopentyl glycol, hexane diol, or the like
  • alicyclic diols e.g., 1,4-cyclohexane dimethanol
  • aromatic diols or the like.
  • a polyester used in the heat shrinkable polyester film of the present invention is preferably a polyester whose glass-transition temperature (Tg) is adjusted to 60°C to 75°C by mixing therein one or more diols whose carbon number is 3 to 6 (e.g., propane diol, butane diol, neopentyl glycol, and hexane diol).
  • Tg glass-transition temperature
  • diols whose carbon number is 3 to 6 (e.g., propane diol, butane diol, neopentyl glycol, and hexane diol).
  • neopentyl glycol as one of the diol components, preferably in an amount of 15 mol% to 25 mol% (this applies to all the diol components used).
  • a diol whose carbon number is 8 or more e.g., octanediol
  • a polyalcohol whose valence is 3 or more e.g., trimethylolpropane, trimethylolethane, glycerin, and diglycerin.
  • the content thereof is preferably 3 mol% or less.
  • the polyester preferably contains the least amount possible of diethylene glycol, triethylene glycol, and polyethylene glycol. Particularly, diethylene glycol is likely to be present because it is a byproduct from a polyester polymerization process. Nevertheless, in the polyester used in the present invention, the content of diethylene glycol is preferably less than 4 mol%.
  • the acid component content or the diol component content is the content with respect to the acid component or the diol component, respectively, of all the polyesters. These contents are irrespective of whether ester interchange occurs after mixing.
  • polyesters can be produced by any conventional method.
  • the polyester can be obtained by using, for example, a direct esterification method, where a dicarboxylic acid and a diol are directly reacted with each other, or a transesterification method, where a dimethyl dicarboxylate and a diol are reacted with each other.
  • the polymerization may be performed either in a batch process or a continuous process.
  • An Abbe refractometer was used to measure the refractive index of the film along the longitudinal, transverse and thickness directions of the film.
  • the refractive index of the film along the longitudinal direction is denoted by Nx
  • the refractive index along the transverse direction is denoted by Ny.
  • the film was rolled into a tubular shape with two of its opposite edges bonded together with 1,3-dioxolane.
  • the tubular film was cut into smaller pieces (samples) each having a width of 15 mm in a transverse direction which is perpendicular to the direction along which the film runs through the processing system.
  • the bonded portion was pulled along the transverse direction and peeled apart.
  • solvent adhesiveness in Table 1, " ⁇ " indicates a sample which had a sufficient peel resistance.
  • each film sample was rolled into a tube 1, with two of its opposite edges being bonded together, and then the tube 1 was placed around a vertical stack 2 (total weight: 660 g) of three food container cans each having a diameter of 72 mm and a height of 55 mm.
  • the can stack 2 with the tube 1 placed therearound was passed through a shrink tunnel to shrink the tube 1 onto the can stack 2.
  • a total of 18 packs of such can stacks 3 were placed into a cardboard box 4 having a length of 455 mm, a width of 230 mm and a height of 165 mm (6 packs in the length direction by 3 packs in the width direction), and the cardboard box 4 was sealed.
  • the cardboard box 4 was vibrated along the longitudinal direction (indicated by arrow A in the figure) for 30 min by a stroke of 50 mm and at a vibration rate of 180 reciprocations/min, after which the transverse tearage of the tube 1 was visually observed.
  • the defect percentage (%) was determined based on the number of defective packs per 18 packs, wherein the defective pack was any pack having a tear flaw 6 whose length ("L" in Figure 3) is 30 mm or longer in a film 7 along a periphery of the can 5. Then, a sample having a defect percentage of 20% or less was marked " ⁇ ", and a sample having a defect percentage exceeding 20% less was marked " ⁇ ".
  • polyesters A-E polyesters A-E were used in the examples and comparative examples to be described below.
  • the undrawn film was drawn in the longitudinal direction by a drawing factor of 1.1 by using a multi-stage roll type vertical drawer (roll temperature: 80°C), and then drawn with a tenter in the transverse direction at the film temperature of 73°C by a drawing factor of 3.9.
  • the film was then subjected to a heat treatment at 82°C for 10 sec to obtain a heat shrinkable polyester film having a thickness of 45 ⁇ m.
  • a heat shrinkable polyester film having a thickness of 45 ⁇ m was obtained in a manner similar to that of Example 1 except that different polyester ratio and drawing conditions were used as shown in Table 1.
  • each of the heat shrinkable polyester films obtained in Examples 1-4 exhibits a good shrunk finish property (no defects such as insufficient shrinkage, crease, distortion are observed), a good solvent adhesiveness, a good shock resistance in the vibration test and a good shock resistance in the actual shipping test.
  • the heat shrinkable polyester film of the present invention is a film having a high quality and a high practicability which is suitable as a multi-packaging label for cans and can be used under low temperatures.
  • the heat shrinkable polyester film of the present invention has a good shock resistance during shipping especially under low temperatures, with a good finish after shrinkage and a sufficient solvent adhesiveness.
  • the heat shrinkable polyester film of the present invention is suitable for use in a multi-packaging label for packaging, inter alia, a stack of cans.

Claims (3)

  1. Film en polyester thermorétractable produit par étirement longitudinal en utilisant un facteur d'étirement de 1,1 à 1,3, à une température de 80 °C à 95 °C, ledit film en polyester thermorétractable ayant un pourcentage de défaut de déchirure transversale de 20 % ou moins, comme déterminé dans l'essai de vibration suivant :
    le film est enroulé selon une forme tubulaire, deux de ses bords opposés étant liés ensemble, puis le film tubulaire est placé autour d'une pile verticale, dont le poids total est de 660 g, de trois boîtes de conserve ayant chacune un diamètre de 72 mm et une hauteur de 55 mm ; la pile de boîtes entourée par le film tubulaire traverse un tunnel de rétraction pour rétracter le film tubulaire sur la pile de boîtes ; un total de 18 paquets de ces piles de boîtes sont placés dans une boîte en carton ayant une longueur de 455 mm, une largeur de 230 mm et une hauteur de 165 mm, 6 paquets dans le sens de la longueur sur 3 paquets dans le sens de la largeur, et la boîte en carton est fermée hermétiquement ; la boîte en carton est amenée à vibrer sur toute sa largeur pendant 30 minutes pour une course de 50 mm, et à une vitesse de vibration de 180 vibrations/min, après quoi la déchirure transversale du film tubulaire est observée visuellement ; et le pourcentage de défaut de déchirure transversale (%) est déterminé en fonction du nombre de paquets défectueux par groupe de 18 paquets, dans lequel le paquet défectueux est tout paquet ayant un défaut de déchirure de 30 mm ou plus le long de la périphérie d'une boîte,
    dans lequel le film a un indice de réfraction longitudinale Nx et un indice de réfraction transversale Ny qui satisfont aux expressions suivantes (1) et (2) : 1 , 561 < Nx < 1 , 566
    Figure imgb0011
    et 0 , 040 < Ny - Nx < 0 , 070
    Figure imgb0012
    dans lequel le film a un retrait de 50 % ou plus le long de sa direction de retrait principale, lorsque le film est placé dans l'eau chaude à 95 °C pendant 10 secondes, et
    dans lequel le film a un retrait de 10 % à 25 % le long d'une direction perpendiculaire à sa direction de retrait principale, lorsque le film est placé dans l'eau chaude à une température de 95 °C pendant 10 secondes.
  2. Film en polyester thermorétractable selon la revendication 1, dans lequel le film a une adhésivité au solvant avec le 1,3-dioxolane.
  3. Film en polyester thermorétractable selon la revendication 1 ou 2, dans lequel le film peut être utilisé comme film pour plusieurs emballages.
EP03015681A 1999-01-28 2000-01-28 Feuille en polyester thermorétractable Expired - Lifetime EP1359184B1 (fr)

Applications Claiming Priority (11)

Application Number Priority Date Filing Date Title
JP2083699 1999-01-28
JP2083699A JP3278058B2 (ja) 1999-01-28 1999-01-28 熱収縮性ポリエステル系フィルム
JP6089899A JP2000254968A (ja) 1999-03-08 1999-03-08 熱収縮性ポリエステル系フィルム
JP6089899 1999-03-08
JP11733999A JP2000309647A (ja) 1999-04-23 1999-04-23 熱収縮性ポリエステル系フィルム
JP11734099 1999-04-23
JP11733999 1999-04-23
JP11733899 1999-04-23
JP11734099A JP2000301609A (ja) 1999-04-23 1999-04-23 熱収縮性ポリエステル系フィルム
JP11733899A JP2000309646A (ja) 1999-04-23 1999-04-23 熱収縮性ポリエステル系フィルム
EP00101814A EP1024162B1 (fr) 1999-01-28 2000-01-28 Feuille en polyester thermorétractable

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
EP00101814A Division EP1024162B1 (fr) 1999-01-28 2000-01-28 Feuille en polyester thermorétractable

Publications (2)

Publication Number Publication Date
EP1359184A1 EP1359184A1 (fr) 2003-11-05
EP1359184B1 true EP1359184B1 (fr) 2007-04-11

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EP00101814A Expired - Lifetime EP1024162B1 (fr) 1999-01-28 2000-01-28 Feuille en polyester thermorétractable
EP03015681A Expired - Lifetime EP1359184B1 (fr) 1999-01-28 2000-01-28 Feuille en polyester thermorétractable

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EP00101814A Expired - Lifetime EP1024162B1 (fr) 1999-01-28 2000-01-28 Feuille en polyester thermorétractable

Country Status (4)

Country Link
US (1) US20050196563A1 (fr)
EP (2) EP1024162B1 (fr)
KR (2) KR100497872B1 (fr)
DE (2) DE60034380T2 (fr)

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KR20000053643A (ko) 2000-08-25
DE60034380T2 (de) 2007-12-13
DE60016641D1 (de) 2005-01-20
DE60034380D1 (de) 2007-05-24
EP1359184A1 (fr) 2003-11-05
EP1024162B1 (fr) 2004-12-15
US20050196563A1 (en) 2005-09-08
EP1024162A2 (fr) 2000-08-02
EP1024162A3 (fr) 2000-10-04
DE60016641T2 (de) 2005-12-15
KR100510753B1 (ko) 2005-08-26
KR100497872B1 (ko) 2005-06-29
KR20030084879A (ko) 2003-11-01

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